Phase transition, surface first-order

An interesting experimental example for a diffusion-controlled adsorption process are the data for aqueous solutions of the long-chain alkanol, dodecanol, an extremely sparely soluble surfactant [232]. As one can see in Fig. 4.32, the dynamic surface pressure curves show a distinct kink point. Such points, which is shifted at lower temperatures to shorter times and disappears at higher temperatures, indicate a main phase transition of first order in the adsorption layer. 

From early LEEM studies by Telieps and Bauer [62], it became obvious that both the (7 X 7) and ( lx 1 ) are clearly separated at the surface as shown in Figure 9.29 the phase transition is first order. In contrast to standard thermodynamic models, this phase coexistence is observed over a broad temperature range near Tc and explained by long-range elastic and electrostatic domain interactions [63]. 

On compression, a gaseous phase may condense to a liquid-expanded, L phase via a first-order transition. This transition is difficult to study experimentally because of the small film pressures involved and the need to avoid any impurities [76,193]. There is ample evidence that the transition is clearly first-order there are discontinuities in v-a plots, a latent heat of vaporization associated with the transition and two coexisting phases can be seen. Also, fluctuations in the surface potential [194] in the two phase region indicate two-phase coexistence. The general situation is reminiscent of three-dimensional vapor-liquid condensation and can be treated by the two-dimensional van der Waals equation (Eq. Ill-104) [195] or statistical mechanical models [191]. 

In sect. 2, we have summarized the general theory of phase transitions with an emphasis on low-dimensional phenomena, which are relevant in surface physics, where a surface acts as a substrate on which a two-dimensional adsorbed layer may undergo phase transitions. In the present section, we consider a different class of surface phase transitions wc assume e.g. a semi-infinite system which may undergo a phase transition in the bulk and ask how the phenomena near the transition are locally modified near the surface, sect. 3.1 considers a bulk transition of second order, while sections 3.2 and 3.4-3.6 consider bulk transitions of first order. In this context, a closer look at the roughening transitions of interfaces is necessary (sect. 3.3). Since all these phenomena have been extensively reviewed recently, we shall be very brief and only try to put the phenomena in perspective. 

The lattice gas approach is valid within certain limits for typical metallic hydrides, binaries as well as ternaries. Deviation from this idealized picture indicates that metallic hydrides are not pure host-guest systems, but real chemical compounds. An important difference between the model of hydrogen as a lattice gas, liquid, or solid and real metal hydrides lies in the nature of the phase transitions. Whereas the crystallization of a material is a first-order transition according to Landau s theory, an order-disorder transition in a hydride can be of first or second order. The structural relationships between ordered and disordered phases of metal hydrides have been proven in many cases by crystallographic group-subgroup relationships, which suggests the possibility of second-order (continuous) phase transitions. However, in many cases hints for a transition of first order were found due to a surface contamination of the sample that kinetically hinders the transition to proceed. 

For both first-order and continuous phase transitions, finite size shifts the transition and rounds it in some way. The shift for first-order transitions arises, crudely, because the chemical potential, like most other properties, has a finite-size correction p(A)-p(oo) C (l/A). An approximate expression for this was derived by Siepmann et al [134]. Therefore, the line of intersection of two chemical potential surfaces Pj(T,P) and pjj T,P) will shift, in general, by an amount 0 IN). The rounding is expected because the partition fiinction only has singularities (and hence produces discontinuous or divergent properties) in tlie limit i—>oo otherwise, it is analytic, so for finite Vthe discontinuities must be smoothed out in some way. The shift for continuous transitions arises because the transition happens when L for the finite system, but when i oo m the infinite system. The rounding happens for the same reason as it does for first-order phase transitions whatever the nature of the divergence in thennodynamic properties (described, typically, by critical exponents) it will be limited by the finite size of the system. 

FIG. 5 Schematic representation of adsorption isotherms in the region of the first-order phase transition on a homogeneous (solid line) and heterogeneous (filled circles) surface. 

An intrinsic surface is built up between both phases in coexistence at a first-order phase transition. For the hard sphere crystal-melt interface [51] density, pressure and stress profiles were calculated, showing that the transition from crystal to fluid occurs over a narrow range of only two to three crystal layers. Crystal growth rate constants of a Lennard-Jones (100) surface [52] were calculated from the fluctuations of interfaces. There is evidence for bcc ordering at the surface of a critical fee nucleus [53]. 

If the surface is nearly covered (0A 1) the reaction will be first-order in the gas phase reactant and zero-order in the adsorbed reactant. On the other hand, if the surface is sparsely covered (0A KAPA) the reaction will be first-order in each species or second-order overall. Since adsorption is virtually always exothermic, the first condition will correspond to low temperature and the second condition to high temperatures. This mechanism thus offers a ready explanation of a transition from first-to second-order reaction with increasing temperature. 

Structural changes on surfaces can often be treated as first-order phase transitions rather than as adsorption process. Nucleation and growth of the new phase are reflected in current transients as well as dynamic STM studies. Nucleation-and-growth leads to so-called rising transients whereas mere adsorption usually results in a monotonously falling transient. In Fig. 10 are shown the current responses to potential steps across all four current peaks in the cyclic voltammogram of Fig. 8a [44], With the exception of peak A, all structural transitions yield rising current transients sug-... 

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